EP4076984B1 - Rubber composition - Google Patents
Rubber composition Download PDFInfo
- Publication number
- EP4076984B1 EP4076984B1 EP20842716.1A EP20842716A EP4076984B1 EP 4076984 B1 EP4076984 B1 EP 4076984B1 EP 20842716 A EP20842716 A EP 20842716A EP 4076984 B1 EP4076984 B1 EP 4076984B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolymer
- rubber composition
- diene
- composition according
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 99
- 229920001971 elastomer Polymers 0.000 title claims description 61
- 229920001577 copolymer Polymers 0.000 claims description 56
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 claims description 52
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 45
- 239000005977 Ethylene Substances 0.000 claims description 42
- UAHWPYUMFXYFJY-UHFFFAOYSA-N myrcene group Chemical group CC(=CCCC(C=C)=C)C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims description 25
- 239000006229 carbon black Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 20
- 229920001195 polyisoprene Polymers 0.000 claims description 17
- 150000002430 hydrocarbons Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 13
- 239000012763 reinforcing filler Substances 0.000 claims description 13
- 244000043261 Hevea brasiliensis Species 0.000 claims description 11
- 229920003052 natural elastomer Polymers 0.000 claims description 11
- 229920001194 natural rubber Polymers 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- 238000006116 polymerization reaction Methods 0.000 description 25
- 239000000806 elastomer Substances 0.000 description 22
- 235000019241 carbon black Nutrition 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 239000000470 constituent Substances 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- KXDANLFHGCWFRQ-UHFFFAOYSA-N magnesium;butane;octane Chemical compound [Mg+2].CCC[CH2-].CCCCCCC[CH2-] KXDANLFHGCWFRQ-UHFFFAOYSA-N 0.000 description 12
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 11
- 150000001993 dienes Chemical class 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229920003244 diene elastomer Polymers 0.000 description 7
- 125000002734 organomagnesium group Chemical group 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 6
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000001282 organosilanes Chemical class 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- JSNRRGGBADWTMC-QINSGFPZSA-N (E)-beta-Farnesene Natural products CC(C)=CCC\C(C)=C/CCC(=C)C=C JSNRRGGBADWTMC-QINSGFPZSA-N 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 125000002015 acyclic group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- -1 alkyl radicals Chemical group 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- YSNRTFFURISHOU-UHFFFAOYSA-N beta-farnesene Natural products C=CC(C)CCC=C(C)CCC=C(C)C YSNRTFFURISHOU-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 2
- 235000005911 diet Nutrition 0.000 description 2
- 230000037213 diet Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
- 238000004701 1H-13C HSQC Methods 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000007987 MES buffer Substances 0.000 description 1
- 238000012565 NMR experiment Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical class [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000002625 beta-farnesene group Chemical group 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005570 heteronuclear single quantum coherence Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VILGDADBAQFRJE-UHFFFAOYSA-N n,n-bis(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SN(SC=3SC4=CC=CC=C4N=3)C(C)(C)C)=NC2=C1 VILGDADBAQFRJE-UHFFFAOYSA-N 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920005690 natural copolymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920006301 statistical copolymer Polymers 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- NESLVXDUKMNMOG-UHFFFAOYSA-N triethoxy-(propyltetrasulfanyl)silane Chemical compound CCCSSSS[Si](OCC)(OCC)OCC NESLVXDUKMNMOG-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000012936 vulcanization activator Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- AUMBZPPBWALQRO-UHFFFAOYSA-L zinc;n,n-dibenzylcarbamodithioate Chemical compound [Zn+2].C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1.C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1 AUMBZPPBWALQRO-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0025—Compositions of the sidewalls
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/27—Amount of comonomer in wt% or mol%
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/32—Glass transition temperature [Tg]
Definitions
- the field of the present invention is that of rubber compositions comprising a highly saturated diene elastomer, in particular compositions intended to be used in a tire, preferably in tire sidewalls.
- a tire usually has two beads intended to come into contact with a rim, a crown composed of at least one crown reinforcement and a tread, two sidewalls, the tire being reinforced by a carcass reinforcement anchored in the two beads.
- a sidewall is an elastomeric layer placed outside the carcass reinforcement relative to the internal cavity of the tire, between the crown and the bead so as to totally or partially cover the area of the carcass reinforcement extending from the top to the rim.
- the different constituent components of the crown, the carcass reinforcement, the beads and the sidewalls are assembled to form a tire tire.
- the assembly step is followed by a bandage shaping step to give the assembly a toric shape before the press cooking step.
- the sidewall of a tire being subjected to deformation cycles such as bending during rolling of the tire, the rubber composition constituting a sidewall of a tire must be both sufficiently flexible and not very hysteretic.
- a rubber composition which constitutes a sidewall must have good ozone resistance properties.
- EP 2 682 423 A1 it was proposed in the document EP 2 682 423 A1 to use ethylene and 1,3-diene copolymer elastomers. Nevertheless, there remains a constant concern to further improve the properties of rubber compositions containing a diene copolymer rich in ethylene, in particular a diene copolymer for which the molar rate of ethylene is greater than 50%.
- This layer is generally a carcass ply or an internal reinforcing rubber whose composition generally comprises a diene elastomeric matrix, generally consisting of natural rubber.
- Another object of the invention is a tire comprising this composition.
- composition based on is meant a composition comprising the mixture and/or the in situ reaction product of the different constituents used, some of these constituents being able to react and/or being intended to react with each other, at least less partially, during the different phases of manufacturing the composition; the composition can thus be in the totally or partially crosslinked state or in the non-crosslinked state.
- the rates of units resulting from the insertion of a monomer into a copolymer are expressed as a molar percentage relative to all the monomer units of the copolymer.
- part by weight per hundred parts by weight of elastomer (or pce) is meant for the purposes of the present invention, the part by mass per hundred parts by mass of elastomer.
- any interval of values designated by the expression "between a and b" represents the range of values going from more than a to less than b (that is to say limits a and b excluded) while any interval of values designated by the expression “from a to b” means the range of values going from a to b (that is to say including the strict limits a and b).
- any interval of values designated by the expression “from a to b” means the range of values going from a to b (that is to say including the strict limits a and b).
- a majority compound we mean in the sense of the present invention, that this compound is the majority among the compounds of the same type in the composition, that is to say that it is the one which represents the greatest quantity by mass among compounds of the same type.
- a majority elastomer is the elastomer representing the greatest mass relative to the total mass of the elastomers in the composition.
- a so-called majority charge is that representing the greatest mass among the charges in the composition.
- a “minority” compound is a compound which does not represent the highest mass fraction great among compounds of the same type.
- majority we mean present at more than 50%, preferably more than 60%, 70%, 80%, 90%, and more preferably the “majority” compound represents 100%.
- the compounds comprising carbon mentioned in the description may be of fossil or biosourced origin. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. This concerns in particular polymers, plasticizers, fillers, etc.
- Tg glass transition temperature values “Tg” described herein are measured in a known manner by DSC (Differential Scanning Calorimetry) according to standard ASTM D3418 (1999).
- the copolymer contains ethylene units which represent between 50% and 95% by moles of the monomer units of the copolymer, that is to say between 50% and 95% by moles of the ethylene units and the units of 1,3 -diene.
- the copolymer contains ethylene units which represent from 60% to 90%, preferably from 70% to 85% by mole, of the monomer units of the copolymer.
- the 1,3-diene of formula (I) is a substituted 1,3 diene, which can give rise to units of 1,2 configuration represented by formula (1), of 3,4 configuration represented by formula (2 ) and configuration 1.4 whose trans form is represented below by the formula (3).
- the ethylene unit is a “-(CH 2 -CH 2 )-” unit.
- the copolymer useful for the purposes of the invention is a copolymer of ethylene and 1,3-diene, which implies that the monomer units of the copolymer are units resulting from the polymerization of ethylene and 1,3-diene. .
- the copolymer therefore comprises ethylene units and 1,3-diene units.
- the 1,3-diene can be a single compound, that is to say a single 1,3-diene of formula (I) or be a mixture of 1, 3-dienes of formula (I), the 1,3-dienes of the mixture differing from each other by the group represented by the symbol R.
- the copolymer useful for the purposes of the invention is advantageously a random copolymer according to one any of the embodiments of the invention.
- the copolymer contains 1,3-diene units of 1,2 or 3,4 configuration which represent more than 50% by mole of the 1,3-diene units.
- the 1,3-diene units are more than 50% by mole of the units of 1,2 configuration or 3,4 configuration.
- the 100% complement by mole of the 1,3-diene units in the copolymer consists of all or part of 1,3-diene units of 1,4 configuration.
- preferably more than half of the units of the 1,3-diene of 1,4 configuration are of 1,4-trans configuration, more preferably all the units of the 1,3-diene of 1,4 configuration are of 1.4-trans configuration.
- the 1,3-diene units are more than 50% in the 1,4 configuration.
- the 1,3-diene units of configuration 1,4 represent more than 50 mol% of the 1,3-diene units.
- the 100% complement by mole of the 1,3-diene units in the copolymer consists of all or part of the 1,3-diene units of configuration 1,2 or 3,4.
- the 1,3-diene units of 1,4 configuration represent more than 70 mol% of the 1,3-diene units.
- more than half of the 1,3-diene units of 1,4 configuration are of 1,4-trans configuration, which means that the 1,3-diene units of 1,4 configuration -trans represent more than 50 mol% of the 1,3-diene units of 1,4 configuration.
- the hydrocarbon chain represented by the symbol R can be an unsaturated chain of 3 to 20 carbon atoms.
- the symbol R represents a hydrocarbon chain having 6 to 16 carbon atoms.
- the hydrocarbon chain represented by the symbol R can be a saturated or unsaturated chain.
- the symbol R represents an aliphatic chain, in which case in formula (I) of 1,3-diene, the hydrocarbon chain represented by the symbol R is an aliphatic hydrocarbon chain. It can be a linear or branched chain, in which case the symbol R represents a linear or branched chain.
- the hydrocarbon chain is acyclic, in which case the symbol R represents an acyclic chain.
- the symbol R represents an unsaturated and branched acyclic hydrocarbon chain.
- the hydrocarbon chain represented by the symbol R is advantageously an unsaturated and branched acyclic chain containing from 3 to 20 carbon atoms, in particular from 6 to 16 carbon atoms.
- the 1,3-diene is myrcene or ⁇ -farnesene.
- the 1,3-diene is myrcene. According to another preferred embodiment of the invention, the 1,3-diene is ⁇ -farnesene.
- the copolymer of ethylene and 1,3-diene has a vitreous temperature lower than -35°C, preferably between -90°C and -35°C.
- substituted fluorenyl groups mention may be made of those substituted by alkyl radicals having 1 to 6 carbon atoms or by aryl radicals having 6 to 12 carbon atoms.
- the choice of radicals is also oriented by the accessibility to the corresponding molecules which are the substituted fluorenes, because the latter are commercially available or easily synthesized.
- Positions 2, 3, 6 and 7 respectively designate the position of the carbon atoms of the rings as shown in the diagram below, position 9 corresponding to the carbon atom to which the bridge P is attached.
- the catalytic system can be prepared in a traditional manner by a process similar to that described in the patent application WO 2007054224 Or WO 2007054223 .
- the organomagnesium and the metallocene are reacted in a hydrocarbon solvent typically at a temperature ranging from 20 to 80°C for a period of between 5 and 60 minutes.
- the catalytic system is generally prepared in a hydrocarbon solvent, aliphatic such as methylcyclohexane or aromatic such as toluene.
- the catalytic system is used as is in the process for synthesizing the copolymer according to the invention.
- the catalytic system can be prepared by a process similar to that described in the patent application WO 2017093654 A1 or in the patent application WO 2018020122 A1 .
- the catalytic system also contains a preformation monomer chosen from a conjugated diene, ethylene or a mixture of ethylene and a conjugated diene, in which case the catalytic system is based at least on metallocene, the organomagnesium and the preformation monomer.
- the organomagnesium and the metallocene are reacted in a hydrocarbon solvent typically at a temperature of 20 to 80°C for 10 to 20 minutes to obtain a first reaction product, then with this first reaction product we react at a temperature ranging from 40 to 90°C for 1h to 12h the preformation monomer chosen from a conjugated diene, ethylene or a mixture of ethylene and a conjugated diene.
- the conjugated diene as preformation monomer is preferably a 1,3-diene such as 1,3-butadiene, isoprene or even a 1,3-diene of formula (I), in particular myrcene or ⁇ -farnesene.
- the catalytic system thus obtained can be used immediately in the process according to the invention or be stored under an inert atmosphere before its use in the process according to the invention.
- the metallocene used to prepare the catalytic system can be in the form of crystallized powder or not, or in the form of single crystals.
- the metallocene can be in a monomeric or dimeric form, these forms depending on the method of preparation of the metallocene, as for example described in the patent application WO 2007054224 Or WO 2007054223 .
- the metallocene can be prepared in a traditional manner by a process similar to that described in the patent application WO 2007054224 Or WO 2007054223 , in particular by reaction under inert and anhydrous conditions of the salt of an alkali metal of the ligand with a rare earth borohydride in a suitable solvent, such as an ether, such as diethyl ether or tetrahydrofuran or any other solvent known to those skilled in the art. art. After reaction, the metallocene is separated from the reaction by-products by techniques known to those skilled in the art, such as filtration or precipitation in a second solvent. The metallocene is finally dried and isolated in solid form.
- a suitable solvent such as an ether, such as diethyl ether or tetrahydrofuran or any other solvent known to those skilled in the art. art.
- the organomagnesium useful for the purposes of the invention has the formula MgR 1 R 2 in which R 1 and R 2 , identical or different, represent a carbon group.
- carbon group we mean a group which contains one or more carbon atoms.
- R 1 and R 2 contain 2 to 10 carbon atoms. More preferably, R 1 and R 2 each represent an alkyl.
- the organomagnesium is advantageously a dialkylmagnesium, better still butylethylmagnesium or butyloctylmagnesium, even better butyloctylmagnesium.
- the molar ratio of the organomagnesium to the metal Nd constituting the metallocene is preferably included in a range ranging from 1 to 100, more preferably is greater than or equal to 1 and less than 10.
- the range of values going from 1 to less than 10 is particularly more favorable for obtaining copolymers of high molar masses.
- the copolymer useful for the purposes of the invention is a copolymer which has a microstructure as defined according to the first variant of the invention, it is prepared according to the process mentioned in the present application using a metallocene of formula (II) in which Cp 1 and Cp 2 , identical or different, are chosen from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula C 13 H 8 .
- a metallocene of formula (II) in which Cp 1 and Cp 2 , identical or different, are chosen from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula C 13 H 8 .
- metallocenes of the following formulas are particularly suitable in which the symbol Flu presents the fluorenyl group of formula C 13 H 8 : [ ⁇ Me 2 SiFlu 2 Nd( ⁇ -BH 4 ) 2 Li(THF) ⁇ 2] ; [Me 2 SiFlu 2 Nd( ⁇ -BH 4 ) 2 Li(THF)]; [Me2SiFlu2Nd( ⁇ ,-BH 4 )(THF)]; [ ⁇ Me 2 SiFlu 2 Nd( ⁇ -BH 4 )(THF) ⁇ 2 ]; [Me 2 SiFlu 2 Nd( ⁇ -BH 4 )].
- the copolymer useful for the purposes of the invention is a copolymer which has a microstructure as defined according to the second variant of the invention, it is prepared according to the process mentioned in the present application using a metallocene of formula (II) in which Cp 1 denotes a cyclopentadienyl group Cp of formula C 5 H 4 and Cp 2 a fluorenyl group Flu of formula C 13 H 8 .
- a metallocene of formula (II) in which Cp 1 denotes a cyclopentadienyl group Cp of formula C 5 H 4 and Cp 2 a fluorenyl group Flu of formula C 13 H 8 .
- the polymerization is preferably carried out in solution, continuously or discontinuously.
- the polymerization solvent may be a hydrocarbon, aromatic or aliphatic solvent.
- polymerization solvent mention may be made of toluene and methylcyclohexane.
- the monomers can be introduced into the reactor containing the polymerization solvent and the catalytic system or conversely the catalytic system can be introduced into the reactor containing the polymerization solvent and the monomers.
- the copolymerization is typically carried out under anhydrous conditions and in the absence of oxygen, possibly in the presence of an inert gas.
- the temperature of polymerization generally varies in a range ranging from 30 to 150°C, preferably from 30 to 120°C.
- the copolymerization is carried out at constant ethylene pressure.
- Polymerization can be stopped by cooling the polymerization medium.
- the polymer can be recovered according to conventional techniques known to those skilled in the art, such as for example by precipitation, by evaporation of the solvent under reduced pressure or by steam stripping.
- the rubber composition according to the invention comprises from 15 to less than 50 phr, preferably from 20 to 45 phr, of a copolymer of ethylene and a 1,3-diene of formula (I) such as defined in any of the embodiments described above, including their variants. It is understood that the copolymer can consist of a mixture of copolymers which differ by their microstructure or by their macrostructure.
- the composition further comprises from 5 to 95 phr of polyisoprene comprising a mass content of 1,4-cis bonds of at least 90% of the mass of the polyisoprene.
- the polyisoprene is a polyisoprene comprising a mass content of 1,4-cis bonds of at least 98% of the mass of the polyisoprene.
- the polyisoprene is chosen from the group consisting of natural rubber, synthetic polyisoprenes and mixtures thereof. More preferably, the polyisoprene is a natural rubber.
- the level of polyisoprene, preferably natural rubber, in the composition according to the invention is included in a range ranging from more than 50 to 85 phr, preferably from 55 to 80 phr.
- composition according to the invention may also comprise a reinforcing filler.
- a reinforcing filler typically consists of nanoparticles whose average size (by mass) is less than one micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm.
- the reinforcing filler may comprise carbon black, silica or a mixture thereof.
- the composition of the first layer of the laminate according to the invention may mainly consist of silica.
- it can be mainly, preferably exclusively, made up of carbon black.
- the reinforcing filler consists of at least 80% by weight, preferably at least 90% by weight of carbon black.
- the reinforcing filler comprises exclusively, that is to say 100% by weight, carbon black.
- the carbon black may be a mixture of different carbon blacks, in which case the carbon black levels relate to all the carbon blacks.
- All carbon blacks are suitable as carbon blacks, in particular blacks conventionally used in tires or their treads.
- the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series (ASTM D-1765-2017 grades), such as for example the blacks N115, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772).
- These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a support for some of the rubber additives used.
- the carbon blacks could for example already be incorporated into the diene elastomer, in particular isoprene in the form of a masterbatch (see for example applications WO97/36724-A2 Or WO99/16600-A1 ).
- the reinforcing filler rate is adjusted by those skilled in the art depending on the use of the rubber composition.
- the level of reinforcing filler, preferably carbon black, in the composition according to the invention is included in a range ranging from 15 to 80 phr, preferably from 20 to 55 phr, preferably from 25 to 45 phr .
- the volume fraction of reinforcing filler, preferably carbon black, in the composition according to the invention is included in a range ranging from 8% to 15%.
- the volume fraction of a constituent in a rubber composition is defined as being the ratio of the volume of this constituent to the volume of all the constituents of the composition, it being understood that the volume of all of the constituents is calculated by adding the volume of each of the constituents of the composition.
- the volume fraction of carbon black in a composition is therefore defined as the ratio of the volume of carbon black to the sum of the volumes of each of the constituents of the composition.
- the volume of a constituent is accessible by the ratio between the mass of the constituent introduced into the rubber composition and the density of the constituent.
- the volume fraction of carbon black for a given rate in pce of carbon black can be adjusted by introducing a plasticizer into the composition.
- any type of precipitated silica is suitable, in particular highly dispersible precipitated silicas (called “HDS” for “highly dispersible” or “highly dispersible silica”).
- HDS highly dispersible precipitated silicas
- These precipitated silicas, whether highly dispersible or not, are well known to those skilled in the art.
- the silicas “Ultrasil ® 5000GR”, “Ultrasil ® 7000GR” from the company Evonik the silicas “Zeosil ® 1085GR”, “Zeosil ® 1115 MP”, “Zeosil ® 1165MP”, “ Zeosil ® Premium 200MP”, “Zeosil ® HRS 1200 MP” from the Solvay Company.
- Non-HDS silica the following commercial silicas can be used: “Ultrasil ® VN2GR” silicas, “Ultrasil ® VN3GR” silicas from the company Evonik, “Zeosil ® 175GR” silica from the company Solvay, “Hi” silicas -Sil EZ120G(-D)”, “Hi-Sil EZ160G(-D)”, “Hi-Sil EZ200G(-D)”, “Hi-Sil 243LD”, “Hi-Sil 210”, “Hi-Sil HDP 320G” from PPG.
- an at least bifunctional coupling agent intended to ensure a sufficient connection, of a chemical and/or physical nature, between the inorganic filler ( surface of its particles) and the diene elastomer.
- at least bifunctional organosilanes or polyorganosiloxanes are used.
- bifunctional is meant a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the diene elastomer.
- such a bifunctional compound may comprise a first functional group comprising a silicon atom, said first functional group being capable of interacting with the hydroxyl groups of an inorganic charge and a second functional group comprising a sulfur atom, said second functional group being capable of interacting with the diene elastomer.
- the organosilanes are chosen from the group consisting of polysulfurized organosilanes (symmetric or asymmetric) such as bis(3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT sold under the name “Si69” by the company Evonik or bis disulfide -(triethoxysilylpropyl), abbreviated TESPD marketed under the name “Si75” by the company Evonik, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, such as S-(3-(triethoxysilyl)propyl)octanethioate marketed by the company Momentive under the name “NXT Silane”. More preferably, the organosilane is a polysulfurized organosilane.
- TESPT bis(3-triethoxysilylpropyl) tetrasulfide
- the content of coupling agent in the composition of the first layer of the laminate of the invention can easily be adjusted by those skilled in the art.
- the level of coupling agent represents 0.5% to 15% by weight relative to the quantity of silica.
- the crosslinking system can be any type of system known to those skilled in the art in the field of rubber compositions for tires. It may in particular be based on sulfur, and/or peroxide and/or bismaleimides.
- the crosslinking system is based on sulfur, we then speak of a vulcanization system.
- the sulfur can be provided in any form, in particular in the form of molecular sulfur, or of a sulfur-donating agent.
- At least one vulcanization accelerator is also preferably present, and, optionally, also preferentially, various known vulcanization activators can be used such as zinc oxide, stearic acid or equivalent compound such as stearic acid salts and salts. transition metals, guanidic derivatives (in particular diphenylguanidine), or even known vulcanization retarders.
- Sulfur is used at a preferential rate of between 0.3 pce and 10 pce, more preferably between 0.3 and 5 pce.
- the primary vulcanization accelerator is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5 phr.
- Any compound capable of acting as an accelerator for the vulcanization of diene elastomers in the presence of sulfur can be used as an accelerator, in particular accelerators of the thiazole type as well as their derivatives, accelerators of the sulfenamide, thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthate types.
- MBTS 2-mercaptobenzothiazyl disulfide
- CBS N-cyclohexyl-2-benzothiazyl sulfenamide
- DCBS N,N-dicyclohexyl- 2-benzothiazyl sulfenamide
- TBBS N-ter-butyl-2-benzothiazyl sulfenamide
- TZTD tetrabenzylthiuram disulfide
- ZBEC zinc dibenzyldithiocarbamate
- the rubber composition useful for the purposes of the invention may also comprise all or part of the usual additives usually used in elastomer compositions intended to be used in a tire, such as for example processing agents, plasticizers, pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants.
- the rubber composition comprises a plasticizer. All plasticizers conventionally used in tires are suitable as plasticizers.
- oils preferably non-aromatic or very weakly aromatic chosen from the group consisting of naphthenic oils, paraffinic oils, MES oils, TDAE oils, vegetable oils, ether plasticizers, ester plasticizers.
- the final composition thus obtained is then calendered for example in the form of a sheet or a plate, in particular for characterization in the laboratory, or even extruded (or co-extruded with another rubber composition) in the form of a semi-finished (or profile) of rubber usable for example as a tire sidewall.
- These products can then be used for the manufacture of tires, according to techniques known to those skilled in the art.
- the composition can be either in the raw state (before crosslinking or vulcanization), or in the cooked state (after crosslinking or vulcanization), and can be a semi-finished product which can be used in a tire.
- the crosslinking (or cooking), where appropriate the vulcanization, is carried out in a known manner at a temperature generally between 130°C and 200°C, for a sufficient time which can vary for example between 5 and 90 min depending in particular on the cooking temperature, the crosslinking system adopted and the crosslinking kinetics of the composition considered.
- the present invention also relates to a tire comprising a rubber composition according to the invention.
- the composition according to the invention is present at least in one sidewall of the tire according to the invention.
- this composition is present exclusively in the sidewalls of the tire.
- the tire according to the invention can be intended to equip motor vehicles of the tourism type, SUV ("Sport Utility Vehicles"), or two wheels (in particular motorcycles), or airplanes, or even industrial vehicles chosen from vans, "Weight -heavy” - that is to say metro, bus, road transport vehicles (trucks, tractors, trailers), off-road vehicles such as agricultural or civil engineering vehicles -, and others.
- SUV Sport Utility Vehicles
- two wheels in particular motorcycles
- airplanes or even industrial vehicles chosen from vans, "Weight -heavy” - that is to say metro, bus, road transport vehicles (trucks, tractors, trailers), off-road vehicles such as agricultural or civil engineering vehicles -, and others.
- the spectral characterization and measurements of the microstructure of the copolymers of ethylene and 1,3-myrcene are carried out by Nuclear Magnetic Resonance (NMR) spectroscopy.
- Spectrometer For these measurements, a Bruker Avance III HD 400 MHz spectrometer is used, equipped with a Bruker cryo-BBFO z-grad 5 mm probe.
- 1H experiments are recorded using a radio frequency pulse with a flip angle of 30°, the number of repetitions is 128 with a recycle delay of 5 seconds.
- the 1H-13C HSQC (Heteronuclear Single Quantum Coherence) and HMBC (Heteronuclear Multiple-Bond Correlation) NMR experiments are recorded with a number of repetitions of 128 and a number of increments of 128. The experiments are carried out at 25°C .
- molar percentage 1H integral of a pattern * 100 / ⁇ (1H integrals of each pattern).
- Table 1 Attribution of 1 H and 13 C signals from Ethylene-Myrcene copolymers ⁇ 1H (ppm) ⁇ 13C (ppm) Group 5.54 146.4 8' 5.07 124.6 3 + 8" 4.97 - 4.79 112.0 9' 4.67 108.5 7 2.06 26.5 4 31.8 5 + 5' + 5" 2.0 - 1.79 44.5 8 1.59 25.9 and 17.0 1 1.2 36.8 - 24.0 CH 2 ethylene
- the glass transition temperature is measured using a differential scanning calorimeter according to standard ASTM D3418 (1999).
- the ethylene, N35 quality, comes from the company Air Liquide and is used without prior purification.
- Myrcene (purity ⁇ 95%) is obtained from Sigma-Aldrich.
- the catalyst system is a preformed catalyst system. It is prepared in methylcyclohexane from a metallocene, [Me 2 SiFlu 2 Nd( ⁇ -BH 4 ) 2 Li(THF)], a co-catalyst, butyloctylmagnesium (BOMAG), and a preformation monomer, 1,3-butadiene, in the contents indicated in Table 2. It is prepared according to a preparation method in accordance with paragraph II. 1 of the patent application WO 2017/093654 .
- the catalyst system is a preformed catalyst system. It is prepared in methylcyclohexane from a metallocene, [Me 2 SiFlu 2 Nd( ⁇ -BH 4 ) 2 Li(THF)], a co-catalyst, butyloctylmagnesium (BOMAG), and a preformation monomer, 1,3-butadiene, in the contents indicated in Table 2. It is prepared according to a preparation method in accordance with paragraph II. 1 of the patent application WO 2017/093654 .
- the rubber compositions were produced as described in point II-5 above.
- the “non-productive” phase was carried out in a 3 liter mixer for 5 minutes, for an average paddle speed of 50 revolutions per minute until reaching a maximum drop temperature of 160°C.
- the “productive” phase was carried out in a cylinder tool at 23°C for 10 minutes.
- the adhesion measurements were carried out using a so-called T-peel test or also called 180° peel.
- the peel specimens were produced by bringing the two layers into contact (the constituent compositions of the layers being in the raw state) whose adhesion must be tested.
- a rupture starter was inserted between the two layers.
- Each of the layers was reinforced by a composite layer which limits the deformation of said layers under tension.
- test piece was heated to 150°C under a pressure of 16 bars for 30 minutes. Strips 30 mm wide were then cut with a paper cutter. The two sides of the rupture starter were then placed in the jaws of an “Instron” brand traction machine. The tests were carried out at 20°C and at a traction speed of 100 mm/min. The tensile forces were recorded and these were standardized by the width of the specimen. We obtained a curve of force per unit of width (in N/mm) as a function of the displacement of the moving crossmember of the traction machine (between 0 and 200 mm). The adhesion value retained corresponds to the propagation of the rupture within the specimen and therefore to the average stabilized value of the curve. The adhesion values of the examples were normalized in relation to the control (base 100). An index greater than 100 indicates greater improvement in adherence.
- compositions C1 to C6, in accordance with the invention were compared to controls T1 to T6 not in accordance with the invention which differ respectively from compositions C1 to C6 only by the nature of the 1,3-diene: 1 .3 diene of formula (I) for compositions C1 to C6 and 1,3-butadiene for compositions T1 to T6 (elastomers E1 and E2 were prepared according to the process described in point III.2 above).
- the natural rubber-based layer on which adhesion was tested corresponds to a composition conventionally used as an internal tire layer, such as a carcass ply or a tread underlayer, comprising 100 phr of natural rubber.
- Table 5 presents the compositions tested (in pce), as well as the results obtained.
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- Tires In General (AREA)
Description
Le domaine de la présente invention est celui des compositions de caoutchouc comportant un élastomère diénique fortement saturé, en particulier des compositions destinées à être utilisées dans un pneumatique, de préférence dans des flancs de pneumatique.The field of the present invention is that of rubber compositions comprising a highly saturated diene elastomer, in particular compositions intended to be used in a tire, preferably in tire sidewalls.
Un pneumatique comporte usuellement deux bourrelets destinés à entrer en contact avec une jante, un sommet composé d'au moins une armature de sommet et une bande de roulement, deux flancs, le pneumatique étant renforcé par une armature de carcasse ancrée dans les deux bourrelets. Un flanc est une couche élastomère disposée à l'extérieur de l'armature de carcasse par rapport à la cavité interne du pneumatique, entre le sommet et le bourrelet de sorte à couvrir totalement ou partiellement la zone de l'armature de carcasse s'étendant du sommet au bourrelet.A tire usually has two beads intended to come into contact with a rim, a crown composed of at least one crown reinforcement and a tread, two sidewalls, the tire being reinforced by a carcass reinforcement anchored in the two beads. A sidewall is an elastomeric layer placed outside the carcass reinforcement relative to the internal cavity of the tire, between the crown and the bead so as to totally or partially cover the area of the carcass reinforcement extending from the top to the rim.
Dans la fabrication conventionnelle d'un pneumatique, les différents composants constitutifs du sommet, de l'armature de carcasse, des bourrelets et des flancs sont assemblés pour former un bandage de pneumatique. L'étape d'assemblage est suivie d'une étape de conformation du bandage pour donner la forme torique à l'assemblage avant l'étape de cuisson sous presse. Le flanc d'un pneumatique étant soumis à des cycles de déformation comme la flexion au cours du roulage du pneumatique, la composition de caoutchouc constitutive d'un flanc d'un pneumatique doit être à la fois suffisamment flexible et peu hystérétique.In the conventional manufacture of a tire, the different constituent components of the crown, the carcass reinforcement, the beads and the sidewalls are assembled to form a tire tire. The assembly step is followed by a bandage shaping step to give the assembly a toric shape before the press cooking step. The sidewall of a tire being subjected to deformation cycles such as bending during rolling of the tire, the rubber composition constituting a sidewall of a tire must be both sufficiently flexible and not very hysteretic.
Le flanc étant aussi exposé à l'action de l'ozone, une composition de caoutchouc qui constitue un flanc doit présenter de bonnes propriétés de résistance à l'ozone. En vue de réduire la sensibilité des flancs de pneumatique à l'ozone, il a été proposé dans le document
En effet, le flanc doit adhérer à la couche sur laquelle il est disposé lors de la confection du pneumatique. Cette couche est généralement une nappe carcasse ou une gomme de renfort interne dont la composition comprend généralement une matrice élastomérique diénique, généralement constituée de caoutchouc naturel.In fact, the sidewall must adhere to the layer on which it is placed during the manufacture of the tire. This layer is generally a carcass ply or an internal reinforcing rubber whose composition generally comprises a diene elastomeric matrix, generally consisting of natural rubber.
Par conséquent, il demeure important que la composition du flanc adhère bien à une composition diénique, en particulier pour améliorer la tenue des interfaces à cuit, et donc la durée de vie du pneumatique.Consequently, it remains important that the composition of the sidewall adheres well to a diene composition, in particular to improve the strength of the baked interfaces, and therefore the lifespan of the tire.
Poursuivant ses recherches, la Demanderesse a découvert que l'utilisation d'un copolymère d'éthylène et d'un 1,3-diène spécifique, permet d'améliorer l'adhésion de la composition sur une composition diénique.Continuing its research, the Applicant discovered that the use of a copolymer of ethylene and a specific 1,3-diene makes it possible to improve the adhesion of the composition to a diene composition.
Ainsi un premier objet de l'invention est une composition de caoutchouc au moins à base de :
- 5 à 95 pce de polyisoprène comportant un taux massique de liaisons 1,4-cis d'au moins 90% de la masse du polyisoprène,
- 5 à 95 pce de copolymère d'éthylène et d'un 1,3-diène de formule (I), les unités éthylène dans le copolymère représentant plus de 50% en mole des unités monomères du copolymère,
CH2=CR-CH=CH2 (I)
le symbole R représentant une chaîne hydrocarbonée ayant 3 à 20 atomes de carbone, et - un système de réticulation.
- 5 to 95 phr of polyisoprene comprising a mass content of 1,4-cis bonds of at least 90% of the mass of the polyisoprene,
- 5 to 95 phr of copolymer of ethylene and a 1,3-diene of formula (I), the ethylene units in the copolymer representing more than 50% by mole of the monomer units of the copolymer,
CH 2 =CR-CH=CH 2 (I)
the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms, and - a crosslinking system.
Un autre objet de l'invention est un pneumatique comprenant cette composition.Another object of the invention is a tire comprising this composition.
Par l'expression « à base de » utilisée pour définir les constituants d'un système catalytique ou d'une composition, on entend le mélange de ces constituants, ou le produit de la réaction d'une partie ou de la totalité de ces constituants entre eux.By the expression “based on” used to define the constituents of a catalytic system or of a composition, we mean the mixture of these constituents, or the product of the reaction of part or all of these constituents. between them.
Par l'expression « composition à base de », il faut entendre une composition comportant le mélange et/ou le produit de réaction in situ des différents constituants utilisés, certains de ces constituants pouvant réagir et/ou étant destinés à réagir entre eux, au moins partiellement, lors des différentes phases de fabrication de la composition ; la composition pouvant ainsi être à l'état totalement ou partiellement réticulé ou à l'état non-réticulé. Sauf indication contraire, les taux des unités résultant de l'insertion d'un monomère dans un copolymère sont exprimés en pourcentage molaire par rapport à la totalité des unités monomères du copolymère.By the expression "composition based on", is meant a composition comprising the mixture and/or the in situ reaction product of the different constituents used, some of these constituents being able to react and/or being intended to react with each other, at least less partially, during the different phases of manufacturing the composition; the composition can thus be in the totally or partially crosslinked state or in the non-crosslinked state. Unless otherwise indicated, the rates of units resulting from the insertion of a monomer into a copolymer are expressed as a molar percentage relative to all the monomer units of the copolymer.
Par l'expression « partie en poids pour cent parties en poids d'élastomère » (ou pce), il faut entendre au sens de la présente invention, la partie, en masse pour cent parties en masse d'élastomère.By the expression “part by weight per hundred parts by weight of elastomer” (or pce), is meant for the purposes of the present invention, the part by mass per hundred parts by mass of elastomer.
Dans la présente, sauf indication expresse différente, tous les pourcentages (%) indiqués sont des pourcentages (%) en masse.Herein, unless expressly stated otherwise, all percentages (%) shown are percentages (%) by mass.
D'autre part, tout intervalle de valeurs désigné par l'expression "entre a et b" représente le domaine de valeurs allant de plus de a à moins de b (c'est-à-dire bornes a et b exclues) tandis que tout intervalle de valeurs désigné par l'expression "de a à b" signifie le domaine de valeurs allant de a jusqu'à b (c'est-à-dire incluant les bornes strictes a et b). Dans la présente, lorsqu'on désigne un intervalle de valeurs par l'expression "de a à b", on désigne également et préférentiellement l'intervalle représenté par l'expression "entre a et b". Lorsqu'on fait référence à un composé "majoritaire", on entend au sens de la présente invention, que ce composé est majoritaire parmi les composés du même type dans la composition, c'est-à-dire que c'est celui qui représente la plus grande quantité en masse parmi les composés du même type. Ainsi, par exemple, un élastomère majoritaire est l'élastomère représentant la plus grande masse par rapport à la masse totale des élastomères dans la composition. De la même manière, une charge dite majoritaire est celle représentant la plus grande masse parmi les charges de la composition. A titre d'exemple, dans un système comprenant un seul élastomère, celui-ci est majoritaire au sens de la présente invention ; et dans un système comprenant deux élastomères, l'élastomère majoritaire représente plus de la moitié de la masse des élastomères. Au contraire, un composé "minoritaire" est un composé qui ne représente pas la fraction massique la plus grande parmi les composés du même type. De préférence par majoritaire, on entend présent à plus de 50%, de préférence plus de 60%, 70%, 80%, 90%, et plus préférentiellement le composé « majoritaire » représente 100%.On the other hand, any interval of values designated by the expression "between a and b" represents the range of values going from more than a to less than b (that is to say limits a and b excluded) while any interval of values designated by the expression "from a to b" means the range of values going from a to b (that is to say including the strict limits a and b). In the present, when we designate an interval of values by the expression "from a to b", we also and preferentially designate the interval represented by the expression "between a and b". When we refer to a "majority" compound, we mean in the sense of the present invention, that this compound is the majority among the compounds of the same type in the composition, that is to say that it is the one which represents the greatest quantity by mass among compounds of the same type. Thus, for example, a majority elastomer is the elastomer representing the greatest mass relative to the total mass of the elastomers in the composition. In the same way, a so-called majority charge is that representing the greatest mass among the charges in the composition. For example, in a system comprising a single elastomer, this is the majority within the meaning of the present invention; and in a system comprising two elastomers, the majority elastomer represents more than half of the mass of the elastomers. On the contrary, a "minority" compound is a compound which does not represent the highest mass fraction great among compounds of the same type. Preferably by majority, we mean present at more than 50%, preferably more than 60%, 70%, 80%, 90%, and more preferably the “majority” compound represents 100%.
Les composés comprenant du carbone mentionnés dans la description peuvent être d'origine fossile ou biosourcés. Dans ce dernier cas, ils peuvent être, partiellement ou totalement, issus de la biomasse ou obtenus à partir de matières premières renouvelables issues de la biomasse. Sont concernés notamment les polymères, les plastifiants, les charges, etc.The compounds comprising carbon mentioned in the description may be of fossil or biosourced origin. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. This concerns in particular polymers, plasticizers, fillers, etc.
Toutes les valeurs de température de transition vitreuse « Tg » décrite dans la présente sont mesurées de manière connue par DSC (Differential Scanning Calorimetry) selon la norme ASTM D3418 (1999).All glass transition temperature values “Tg” described herein are measured in a known manner by DSC (Differential Scanning Calorimetry) according to standard ASTM D3418 (1999).
Selon l'invention, la composition comprend de 5 à 95 pce de copolymère d'éthylène et d'un 1,3-diène de formule (I), les unités éthylène dans le copolymère représentant plus de 50% en mole des unités monomères du copolymère,
CH2=CR-CH=CH2 (I)
le symbole R représentant une chaîne hydrocarbonée ayant 3 à 20 atomes de carbone.According to the invention, the composition comprises from 5 to 95 phr of copolymer of ethylene and a 1,3-diene of formula (I), the ethylene units in the copolymer representing more than 50% by mole of the monomer units of the copolymer,
CH2=CR-CH=CH2 (I)
the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms.
De préférence, le copolymère contient des unités éthylène qui représentent entre 50% et 95% en moles des unités monomères du copolymère, c'est-à-dire entre 50% et 95% en moles des unités éthylène et des unités du 1,3-diène. De manière très préférentielle, le copolymère contient des unités éthylène qui représentent de 60% à 90%, de préférence de 70% à 85% en moles, des unités monomères du copolymère.Preferably, the copolymer contains ethylene units which represent between 50% and 95% by moles of the monomer units of the copolymer, that is to say between 50% and 95% by moles of the ethylene units and the units of 1,3 -diene. Very preferably, the copolymer contains ethylene units which represent from 60% to 90%, preferably from 70% to 85% by mole, of the monomer units of the copolymer.
Le 1,3-diène de formule (I) est un 1,3 diène substitué, qui peut donner lieu à des unités de configuration 1,2 représentée par la formule (1), de configuration 3,4 représentée par la formule (2) et de configuration 1,4 dont la forme trans est représentée ci-après par la formule (3).
Comme cela est également bien connu, l'unité éthylène est une unité de motif « -(CH2-CH2)- ».As is also well known, the ethylene unit is a “-(CH 2 -CH 2 )-” unit.
Le copolymère utile aux besoins de l'invention est un copolymère d'éthylène et du 1,3-diène, ce qui implique que les unités monomères du copolymère sont des unités résultant de la polymérisation de l'éthylène et du 1,3-diène. Le copolymère comprend donc des unités éthylène et des unités du 1,3-diène. Selon l'invention, le 1,3-diène peut être un seul composé, c'est-à-dire un seul (en anglais « one ») 1,3-diène de formule (I) ou être un mélange de 1,3-diènes de formule (I), les 1,3-diènes du mélange se différenciant les uns des autres par le groupe représenté par le symbole R. Le copolymère utile aux besoins de l'invention est avantageusement un copolymère statistique selon l'un quelconque des modes de réalisation de l'invention.The copolymer useful for the purposes of the invention is a copolymer of ethylene and 1,3-diene, which implies that the monomer units of the copolymer are units resulting from the polymerization of ethylene and 1,3-diene. . The copolymer therefore comprises ethylene units and 1,3-diene units. According to the invention, the 1,3-diene can be a single compound, that is to say a single 1,3-diene of formula (I) or be a mixture of 1, 3-dienes of formula (I), the 1,3-dienes of the mixture differing from each other by the group represented by the symbol R. The copolymer useful for the purposes of the invention is advantageously a random copolymer according to one any of the embodiments of the invention.
Selon une première variante de l'invention, le copolymère contient des unités du 1,3-diène de configuration 1,2 ou 3,4 qui représentent plus de 50% en mole des unités du 1,3-diène. En d'autres termes, dans le copolymère les unités du 1,3-diène sont à plus de 50% en mole des unités de configuration 1,2 ou de configuration 3,4. Dans cette variante, le complément à 100% en mole des unités du 1,3-diène dans le copolymère est constitué tout ou partie d'unités du 1,3-diène de configuration 1,4. Selon cette première variante, préférentiellement plus de la moitié des unités du 1,3-diène de configuration 1,4 sont de configuration 1,4-trans, plus préférentiellement toutes les unités du 1,3-diène de configuration 1,4 sont de configuration 1,4-trans.According to a first variant of the invention, the copolymer contains 1,3-diene units of 1,2 or 3,4 configuration which represent more than 50% by mole of the 1,3-diene units. In other words, in the copolymer the 1,3-diene units are more than 50% by mole of the units of 1,2 configuration or 3,4 configuration. In this variant, the 100% complement by mole of the 1,3-diene units in the copolymer consists of all or part of 1,3-diene units of 1,4 configuration. According to this first variant, preferably more than half of the units of the 1,3-diene of 1,4 configuration are of 1,4-trans configuration, more preferably all the units of the 1,3-diene of 1,4 configuration are of 1.4-trans configuration.
Selon une deuxième variante de l'invention, dans le copolymère les unités du 1,3-diène sont à plus de 50% de configuration 1,4. En d'autres termes, les unités du 1,3-diène de configuration 1,4 représentent plus de 50% en mole des unités du 1,3-diène. Dans cette variante, le complément à 100% en mole des unités du 1,3-diène dans le copolymère est constitué tout ou partie d'unités du 1,3-diène de configuration 1,2 ou 3,4. De préférence, les unités du 1,3-diène de configuration 1,4 représentent plus de 70% en mole des unités du 1,3-diène. Avantageusement, les unités du 1,3-diène de configuration 1,4 sont pour plus de la moitié d'entre elles de configuration 1,4-trans, ce qui signifie que les unités du 1,3-diène de configuration 1,4-trans représentent plus de 50% en mole des unités du 1,3-diène de configuration 1,4.According to a second variant of the invention, in the copolymer the 1,3-diene units are more than 50% in the 1,4 configuration. In other words, the 1,3-diene units of configuration 1,4 represent more than 50 mol% of the 1,3-diene units. In this variant, the 100% complement by mole of the 1,3-diene units in the copolymer consists of all or part of the 1,3-diene units of configuration 1,2 or 3,4. Preferably, the 1,3-diene units of 1,4 configuration represent more than 70 mol% of the 1,3-diene units. Advantageously, more than half of the 1,3-diene units of 1,4 configuration are of 1,4-trans configuration, which means that the 1,3-diene units of 1,4 configuration -trans represent more than 50 mol% of the 1,3-diene units of 1,4 configuration.
Quelle que soit la variante précitée, dans la formule (I) du 1,3-diène, la chaîne hydrocarbonée représentée par le symbole R peut être une chaîne insaturée de 3 à 20 atomes de carbone. De préférence, le symbole R représente une chaîne hydrocarbonée ayant 6 à 16 atomes de carbone.Whatever the aforementioned variant, in formula (I) of 1,3-diene, the hydrocarbon chain represented by the symbol R can be an unsaturated chain of 3 to 20 carbon atoms. Preferably, the symbol R represents a hydrocarbon chain having 6 to 16 carbon atoms.
La chaîne hydrocarbonée représentée par le symbole R peut être une chaîne saturée ou insaturée. De préférence, le symbole R représente une chaîne aliphatique, auquel cas dans la formule (I) du 1,3-diène, la chaîne hydrocarbonée représentée par le symbole R est une chaîne hydrocarbonée aliphatique. Elle peut être une chaîne linéaire ou ramifiée, auquel cas le symbole R représente une chaîne linéaire ou ramifiée. De préférence, la chaîne hydrocarbonée est acyclique, auquel cas le symbole R représente une chaîne acyclique. De préférence, le symbole R représente une chaîne hydrocarbonée acyclique insaturée et ramifiée. La chaîne hydrocarbonée représentée par le symbole R est avantageusement une chaîne acyclique insaturée et ramifiée contenant de 3 à 20 atomes de carbone, en particulier de 6 à 16 atomes de carbone. Très avantageusement, le 1,3-diène est le myrcène ou le β-farnésène.The hydrocarbon chain represented by the symbol R can be a saturated or unsaturated chain. Preferably, the symbol R represents an aliphatic chain, in which case in formula (I) of 1,3-diene, the hydrocarbon chain represented by the symbol R is an aliphatic hydrocarbon chain. It can be a linear or branched chain, in which case the symbol R represents a linear or branched chain. Preferably, the hydrocarbon chain is acyclic, in which case the symbol R represents an acyclic chain. Preferably, the symbol R represents an unsaturated and branched acyclic hydrocarbon chain. The hydrocarbon chain represented by the symbol R is advantageously an unsaturated and branched acyclic chain containing from 3 to 20 carbon atoms, in particular from 6 to 16 carbon atoms. Very advantageously, the 1,3-diene is myrcene or β-farnesene.
Selon un mode de réalisation préférentiel de l'invention, le 1,3-diène est le myrcène. Selon un autre mode de réalisation préférentiel de l'invention, le 1,3-diène est le β-farnésène.According to a preferred embodiment of the invention, the 1,3-diene is myrcene. According to another preferred embodiment of the invention, the 1,3-diene is β-farnesene.
De préférence, le copolymère d'éthylène et du 1,3-diène présente une température de vitreuse inférieure à -35°C, de préférence comprise entre -90°C et -35°C.Preferably, the copolymer of ethylene and 1,3-diene has a vitreous temperature lower than -35°C, preferably between -90°C and -35°C.
Le copolymère peut être préparé par un procédé qui comprend la copolymérisation d'éthylène et du 1,3-diène en présence d'un système catalytique à base au moins d'un métallocène de formule (II) et d'un organomagnésien de formule (III)
P(Cp1Cp2) Nd(BH4)(1+y)-Ly-Nx (II)
MgR1R2 (III)
dans lesquels :
- Cp1 et Cp2, identiques ou différents, étant choisis dans le groupe constitué par le groupe cyclopentadiényle de formule C5H4 , le groupe fluorényle non substitué de formule C13H8 et les groupes fluorényles substitués,
- P étant un groupe pontant les deux groupes Cp1 et Cp2 et représentant un groupe ZR3R4, Z représentant un atome de silicium ou de carbone, R3 et R4, identiques ou différents, représentant chacun un groupe alkyle comprenant de 1 à 20 atomes de carbone, de préférence un méthyle,
- y, nombre entier, étant égal ou supérieur à 0,
- x, nombre entier ou non, étant égal ou supérieur à 0,
- L représentant un métal alcalin choisi dans le groupe constitué par le lithium, le sodium et le potassium,
- N représentant une molécule d'un éther, de préférence diéthyléther ou tétrahydrofuranne,
- R1 et R2, identiques ou différents, représentant un groupe carboné.
P(Cp 1 Cp 2 ) Nd(BH 4 ) (1+y)- L y -N x (II)
MgR 1 R 2 (III)
wherein :
- Cp 1 and Cp 2 , identical or different, being chosen from the group consisting of the cyclopentadienyl group of formula C 5 H 4 , the unsubstituted fluorenyl group of formula C 13 H 8 and substituted fluorenyl groups,
- P being a group bridging the two groups Cp 1 and Cp 2 and representing a ZR 3 R 4 group, Z representing a silicon or carbon atom, R 3 and R 4 , identical or different, each representing an alkyl group comprising 1 with 20 carbon atoms, preferably methyl,
- y, integer, being equal to or greater than 0,
- x, integer or not, being equal to or greater than 0,
- L representing an alkali metal chosen from the group consisting of lithium, sodium and potassium,
- N representing a molecule of an ether, preferably diethyl ether or tetrahydrofuran,
- R 1 and R 2 , identical or different, representing a carbon group.
A titre de groupes fluorényles substitués, on peut citer ceux substitués par des radicaux alkyles ayant 1 à 6 atomes de carbone ou par des radicaux aryles ayant 6 à 12 atomes de carbone. Le choix des radicaux est aussi orienté par l'accessibilité aux molécules correspondantes que sont les fluorènes substitués, parce que ces derniers sont disponibles commercialement ou facilement synthétisables.As substituted fluorenyl groups, mention may be made of those substituted by alkyl radicals having 1 to 6 carbon atoms or by aryl radicals having 6 to 12 carbon atoms. The choice of radicals is also oriented by the accessibility to the corresponding molecules which are the substituted fluorenes, because the latter are commercially available or easily synthesized.
A titre de groupes fluorényles substitués, on peut citer plus particulièrement les groupes 2,7-ditertiobutyle-fluorényle et 3,6-ditertiobutyle-fluorényle. Les positions 2, 3, 6 et 7 désignent respectivement la position des atomes de carbone des cycles comme cela est représenté dans le schéma ci-après, la position 9 correspondant à l'atome de carbone auquel est attaché le pont P.
Le système catalytique peut être préparé de façon traditionnelle par un procédé analogue à celui décrit dans la demande de brevet
Alternativement, le système catalytique peut être préparé par un procédé analogue à celui décrit dans la demande de brevet
Le métallocène utilisé pour préparer le système catalytique peut se trouver sous la forme de poudre cristallisée on non, ou encore sous la forme de monocristaux. Le métallocène peut se présenter sous une forme monomère ou dimère, ces formes dépendant du mode de préparation du métallocène, comme par exemple cela est décrit dans la demande de brevet
Comme toute synthèse faite en présence de composé organométallique, la synthèse du métallocène et celle du système catalytique ont lieu dans des conditions anhydres sous atmosphère inerte. Typiquement, les réactions sont conduites à partir de solvants et de composés anhydres sous azote ou argon anhydre.Like any synthesis carried out in the presence of an organometallic compound, the synthesis of the metallocene and that of the catalytic system take place in anhydrous conditions under an inert atmosphere. Typically, reactions are carried out using solvents and anhydrous compounds under anhydrous nitrogen or argon.
L'organomagnésien utile aux besoins de l'invention est de formule MgR1R2 dans laquelle R1 et R2, identiques ou différents, représentent un groupe carboné. On entend par groupe carboné un groupe qui contient un ou plusieurs atomes de carbone. De préférence, R1 et R2 contiennent 2 à 10 atomes de carbone. De manière plus préférentielle, R1 et R2 représentent chacun un alkyle. L'organomagnésien est avantageusement un dialkylmagnésien, mieux le butyléthylmagnésium ou le butyloctylmagnésium, encore mieux le butyloctylmagnésium.The organomagnesium useful for the purposes of the invention has the formula MgR 1 R 2 in which R 1 and R 2 , identical or different, represent a carbon group. By carbon group we mean a group which contains one or more carbon atoms. Preferably, R 1 and R 2 contain 2 to 10 carbon atoms. More preferably, R 1 and R 2 each represent an alkyl. The organomagnesium is advantageously a dialkylmagnesium, better still butylethylmagnesium or butyloctylmagnesium, even better butyloctylmagnesium.
Selon l'un quelconque des modes de réalisation de l'invention, le rapport molaire de l'organomagnésien sur le métal Nd constituant le métallocène est de préférence compris dans un domaine allant de 1 à 100, de manière plus préférentielle est supérieur ou égal à 1 et inférieur à 10. La plage de valeurs allant de 1 à moins de 10 est notamment plus favorable pour l'obtention de copolymères de masses molaires élevées.According to any one of the embodiments of the invention, the molar ratio of the organomagnesium to the metal Nd constituting the metallocene is preferably included in a range ranging from 1 to 100, more preferably is greater than or equal to 1 and less than 10. The range of values going from 1 to less than 10 is particularly more favorable for obtaining copolymers of high molar masses.
Lorsque le copolymère utile aux besoins de l'invention est un copolymère qui a une microstructure telle que définie selon la première variante de l'invention, il est préparé selon le procédé mentionné dans la présente demande en utilisant un métallocène de formule (II) dans laquelle Cp1 et Cp2, identiques ou différents, sont choisis dans le groupe constitué par les groupes fluorényles substitués et le groupe fluorényle non substitué de formule C13H8. Pour cette variante, conviennent en particulier les métallocènes de formules suivantes dans lesquelles le symbole Flu présente le groupe fluorényle de formule C13H8 : [{Me2SiFlu2Nd(µ-BH4)2Li(THF)}2]; [Me2SiFlu2Nd(µ-BH4)2Li(THF)]; [Me2SiFlu2Nd(µ,-BH4)(THF)] ; [{Me2SiFlu2Nd(µ-BH4)(THF)}2] ; [Me2SiFlu2Nd(µ-BH4)].When the copolymer useful for the purposes of the invention is a copolymer which has a microstructure as defined according to the first variant of the invention, it is prepared according to the process mentioned in the present application using a metallocene of formula (II) in which Cp 1 and Cp 2 , identical or different, are chosen from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula C 13 H 8 . For this variant, metallocenes of the following formulas are particularly suitable in which the symbol Flu presents the fluorenyl group of formula C 13 H 8 : [{Me 2 SiFlu 2 Nd(µ-BH 4 ) 2 Li(THF)} 2] ; [Me 2 SiFlu 2 Nd(µ-BH 4 ) 2 Li(THF)]; [Me2SiFlu2Nd(µ,-BH 4 )(THF)]; [{Me 2 SiFlu 2 Nd(µ-BH 4 )(THF)} 2 ]; [Me 2 SiFlu 2 Nd(µ-BH 4 )].
Lorsque le copolymère utile aux besoins de l'invention est un copolymère qui a une microstructure telle que définie selon la deuxième variante de l'invention, il est préparé selon le procédé mentionné dans la présente demande en utilisant un métallocène de formule (II) dans laquelle Cp1 désigne un groupe cyclopentadiényle Cp de formule C5H4 et Cp2 un groupe fluorényle Flu de formule C13H8.When the copolymer useful for the purposes of the invention is a copolymer which has a microstructure as defined according to the second variant of the invention, it is prepared according to the process mentioned in the present application using a metallocene of formula (II) in which Cp 1 denotes a cyclopentadienyl group Cp of formula C 5 H 4 and Cp 2 a fluorenyl group Flu of formula C 13 H 8 .
L'homme du métier sait adapter aussi les conditions de polymérisation et les concentrations en chacun des réactifs (constituants du système catalytique, monomères) selon le matériel (outils, réacteurs) utilisé pour conduire la polymérisation et les différentes réactions chimiques. Comme cela est connu de l'homme du métier, la copolymérisation ainsi que la manipulation des monomères, du système catalytique et du ou des solvants de polymérisation se font dans des conditions anhydres et sous atmosphère inerte. Les solvants de polymérisation sont typiquement des solvants hydrocarbonés, aliphatiques ou aromatiques.Those skilled in the art also know how to adapt the polymerization conditions and the concentrations of each of the reagents (constituents of the catalytic system, monomers) according to the equipment (tools, reactors) used to carry out the polymerization and the different chemical reactions. As is known to those skilled in the art, the copolymerization as well as the handling of the monomers, the catalytic system and the polymerization solvent(s) are carried out under anhydrous conditions and under an inert atmosphere. Polymerization solvents are typically hydrocarbon, aliphatic or aromatic solvents.
La polymérisation est conduite de préférence en solution, en continu ou discontinu. Le solvant de polymérisation peut être un solvant hydrocarboné, aromatique ou aliphatique. A titre d'exemple de solvant de polymérisation, on peut citer le toluène et le méthylcyclohexane. Les monomères peuvent être introduits dans le réacteur contenant le solvant de polymérisation et le système catalytique ou inversement le système catalytique peut être introduit dans le réacteur contenant le solvant de polymérisation et les monomères. La copolymérisation est conduite typiquement dans des conditions anhydres et en l'absence d'oxygène, en présence éventuelle d'un gaz inerte. La température de polymérisation varie généralement dans un domaine allant de 30 à 150°C, préférentiellement de 30 à 120°C. De préférence, la copolymérisation est conduite à pression constante d'éthylène.The polymerization is preferably carried out in solution, continuously or discontinuously. The polymerization solvent may be a hydrocarbon, aromatic or aliphatic solvent. As an example of polymerization solvent, mention may be made of toluene and methylcyclohexane. The monomers can be introduced into the reactor containing the polymerization solvent and the catalytic system or conversely the catalytic system can be introduced into the reactor containing the polymerization solvent and the monomers. The copolymerization is typically carried out under anhydrous conditions and in the absence of oxygen, possibly in the presence of an inert gas. The temperature of polymerization generally varies in a range ranging from 30 to 150°C, preferably from 30 to 120°C. Preferably, the copolymerization is carried out at constant ethylene pressure.
Au cours de la polymérisation de l'éthylène et du 1,3-diène dans un réacteur de polymérisation, un ajout continu d'éthylène et du 1,3-diène peut être réalisé dans le réacteur de polymérisation, auquel cas le réacteur de polymérisation est un réacteur alimenté. Ce mode de réalisation est tout particulièrement adapté pour la synthèse de copolymère statistique.During the polymerization of ethylene and 1,3-diene in a polymerization reactor, continuous addition of ethylene and 1,3-diene can be carried out in the polymerization reactor, in which case the polymerization reactor is a powered reactor. This embodiment is particularly suitable for the synthesis of statistical copolymers.
La polymérisation peut être stoppée par refroidissement du milieu de polymérisation. Le polymère peut être récupéré selon les techniques classiques connues de l'homme du métier comme par exemple par précipitation, par évaporation du solvant sous pression réduite ou par stripping à la vapeur d'eau.Polymerization can be stopped by cooling the polymerization medium. The polymer can be recovered according to conventional techniques known to those skilled in the art, such as for example by precipitation, by evaporation of the solvent under reduced pressure or by steam stripping.
De préférence, la composition de caoutchouc selon l'invention comprend de 15 à moins de 50 pce, de préférence de 20 à 45 pce, d'un copolymère d'éthylène et d'un 1,3-diène de formule (I) tel que défini dans l'un des quelconques modes de réalisation décrits précédemment, y compris leurs variantes. Il est entendu que le copolymère peut être constitué par un mélange de copolymères qui se différencient par leur microstructure ou par leur macrostructure.Preferably, the rubber composition according to the invention comprises from 15 to less than 50 phr, preferably from 20 to 45 phr, of a copolymer of ethylene and a 1,3-diene of formula (I) such as defined in any of the embodiments described above, including their variants. It is understood that the copolymer can consist of a mixture of copolymers which differ by their microstructure or by their macrostructure.
Selon l'invention, la composition comprend en outre de 5 à 95 pce de polyisoprène comportant un taux massique de liaisons 1,4-cis d'au moins 90% de la masse du polyisoprène.According to the invention, the composition further comprises from 5 to 95 phr of polyisoprene comprising a mass content of 1,4-cis bonds of at least 90% of the mass of the polyisoprene.
Avantageusement, le polyisoprène est un polyisoprène comportant un taux massique de liaisons 1,4-cis d'au moins 98%, de la masse du polyisoprène.Advantageously, the polyisoprene is a polyisoprene comprising a mass content of 1,4-cis bonds of at least 98% of the mass of the polyisoprene.
De préférence, le polyisoprène est choisi dans le groupe constitué par le caoutchouc naturel, les polyisoprènes de synthèse et leurs mélanges. De préférence encore le polyisoprène est un caoutchouc naturel.Preferably, the polyisoprene is chosen from the group consisting of natural rubber, synthetic polyisoprenes and mixtures thereof. More preferably, the polyisoprene is a natural rubber.
Avantageusement, le taux du polyisoprène, de préférence de caoutchouc naturel, dans la composition selon l'invention est compris dans un domaine allant de plus de 50 à 85 pce, de préférence de 55 à 80 pce.Advantageously, the level of polyisoprene, preferably natural rubber, in the composition according to the invention is included in a range ranging from more than 50 to 85 phr, preferably from 55 to 80 phr.
La composition selon l'invention peut en outre comprendre une charge renforçante. Une telle charge renforçante consiste typiquement en des nanoparticules dont la taille moyenne (en masse) est inférieure au micromètre, généralement inférieure à 500 nm, le plus souvent comprise entre 20 et 200 nm, en particulier et plus préférentiellement comprise entre 20 et 150 nm.The composition according to the invention may also comprise a reinforcing filler. Such a reinforcing filler typically consists of nanoparticles whose average size (by mass) is less than one micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm.
La charge renforçante peut comprendre du noir de carbone, de la silice ou un de leurs mélanges. La composition de la première couche du stratifié selon l'invention peut être majoritairement constituée de silice. De préférence, elle peut être majoritairement, de préférence exclusivement, constituée de noir de carbone. De préférence encore, la charge renforçante est constituée d'au moins 80% en poids, de préférence d'au moins 90% en poids de noir de carbone. De préférence, la charge renforçante comprend exclusivement, c'est-à-dire 100% en poids, de noir de carbone. Le noir de carbone peut être un mélange de différents noirs de carbone, auquel cas les taux de noir de carbone se rapportent à l'ensemble des noirs de carbone.The reinforcing filler may comprise carbon black, silica or a mixture thereof. The composition of the first layer of the laminate according to the invention may mainly consist of silica. Preferably, it can be mainly, preferably exclusively, made up of carbon black. More preferably, the reinforcing filler consists of at least 80% by weight, preferably at least 90% by weight of carbon black. Preferably, the reinforcing filler comprises exclusively, that is to say 100% by weight, carbon black. The carbon black may be a mixture of different carbon blacks, in which case the carbon black levels relate to all the carbon blacks.
Comme noirs de carbone conviennent tous les noirs de carbone, notamment les noirs conventionnellement utilisés dans les pneumatiques ou leurs bandes de roulement. Parmi ces derniers, on citera plus particulièrement les noirs de carbone renforçants des séries 100, 200, 300, ou les noirs de série 500, 600 ou 700 (grades ASTM D-1765-2017), comme par exemple les noirs N115, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772). Ces noirs de carbone peuvent être utilisés à l'état isolé, tels que disponibles commercialement, ou sous tout autre forme, par exemple comme support de certains des additifs de caoutchouterie utilisés. Les noirs de carbone pourraient être par exemple déjà incorporés à l'élastomère diénique, notamment isoprénique sous la forme d'un masterbatch (voir par exemple demandes
Le taux de charge renforçante est ajusté par l'homme du métier en fonction de l'usage de la composition de caoutchouc. Avantageusement, le taux de charge renforçante, de préférence de noir de carbone, dans la composition selon l'invention, est compris dans un domaine allant de 15 à 80 pce, de préférence de 20 à 55 pce, de préférence de 25 à 45 pce.The reinforcing filler rate is adjusted by those skilled in the art depending on the use of the rubber composition. Advantageously, the level of reinforcing filler, preferably carbon black, in the composition according to the invention, is included in a range ranging from 15 to 80 phr, preferably from 20 to 55 phr, preferably from 25 to 45 phr .
De préférence également, la fraction volumique de charge renforçante, de préférence de noir de carbone, dans la composition selon l'invention est comprise dans un domaine allant de 8% à 15%. De manière connue, la fraction volumique d'un constituant dans une composition de caoutchouc est définie comme étant le rapport du volume de ce constituant sur le volume de l'ensemble des constituants de la composition, étant entendu que le volume de l'ensemble des constituants est calculé en additionnant le volume de chacun des constituants de la composition. La fraction volumique de noir de carbone dans une composition est donc définie comme le rapport du volume de noir de carbone sur la somme des volumes de chacun des constituants de la composition. Le volume d'un constituant est accessible par le ratio entre la masse du constituant introduit dans la composition de caoutchouc et la densité du constituant. De manière connue, la fraction volumique de noir de carbone pour un taux donné en pce de noir de carbone peut être ajustée par l'introduction dans la composition d'un plastifiant.Also preferably, the volume fraction of reinforcing filler, preferably carbon black, in the composition according to the invention is included in a range ranging from 8% to 15%. In known manner, the volume fraction of a constituent in a rubber composition is defined as being the ratio of the volume of this constituent to the volume of all the constituents of the composition, it being understood that the volume of all of the constituents is calculated by adding the volume of each of the constituents of the composition. The volume fraction of carbon black in a composition is therefore defined as the ratio of the volume of carbon black to the sum of the volumes of each of the constituents of the composition. The volume of a constituent is accessible by the ratio between the mass of the constituent introduced into the rubber composition and the density of the constituent. In known manner, the volume fraction of carbon black for a given rate in pce of carbon black can be adjusted by introducing a plasticizer into the composition.
Comme silices conviennent tout type de silice précipitée, notamment des silices précipitées hautement dispersibles (dites « HDS » pour « highly dispersible » ou « highly dispersible silica »). Ces silices précipitées, hautement dispersibles ou non, sont bien connues de l'homme du métier. On peut citer, par exemple, les silices décrites dans les demandes
Pour coupler la silice à l'élastomère diénique, on peut utiliser de manière bien connue un agent de couplage (ou agent de liaison) au moins bifonctionnel destiné à assurer une connexion suffisante, de nature chimique et/ou physique, entre la charge inorganique (surface de ses particules) et l'élastomère diénique. On utilise en particulier des organosilanes ou des polyorganosiloxanes au moins bifonctionnels. Par « bifonctionnel », on entend un composé possédant un premier groupe fonctionnel capable d'interagir avec la charge inorganique et un second groupe fonctionnel capable d'interagir avec l'élastomère diénique. Par exemple, un tel composé bifonctionnel peut comprendre un premier groupe fonctionnel comprenant un atome de silicium, le dit premier groupe fonctionnel étant apte à interagir avec les groupes hydroxyles d'une charge inorganique et un second groupe fonctionnel comprenant un atome de soufre, le dit second groupe fonctionnel étant apte à interagir avec l'élastomère diénique.To couple the silica to the diene elastomer, it is possible to use in a well-known manner an at least bifunctional coupling agent (or bonding agent) intended to ensure a sufficient connection, of a chemical and/or physical nature, between the inorganic filler ( surface of its particles) and the diene elastomer. In particular, at least bifunctional organosilanes or polyorganosiloxanes are used. By “bifunctional” is meant a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the diene elastomer. For example, such a bifunctional compound may comprise a first functional group comprising a silicon atom, said first functional group being capable of interacting with the hydroxyl groups of an inorganic charge and a second functional group comprising a sulfur atom, said second functional group being capable of interacting with the diene elastomer.
Préférentiellement, les organosilanes sont choisis dans le groupe constitué par les organosilanes polysulfurés (symétriques ou asymétriques) tels que le tétrasulfure de bis(3-triéthoxysilylpropyl), en abrégé TESPT commercialisé sous la dénomination « Si69 » par la société Evonik ou le disulfure de bis-(triéthoxysilylpropyle), en abrégé TESPD commercialisé sous la dénomination « Si75 » par la société Evonik, les polyorganosiloxanes, les mercaptosilanes, les mercaptosilanes bloqués, tels que l'octanethioate de S-(3-(triéthoxysilyl)propyle)commercialisé par la société Momentive sous la dénomination « NXT Silane ». Plus préférentiellement, l'organosilane est un organosilane polysulfuré.Preferably, the organosilanes are chosen from the group consisting of polysulfurized organosilanes (symmetric or asymmetric) such as bis(3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT sold under the name “Si69” by the company Evonik or bis disulfide -(triethoxysilylpropyl), abbreviated TESPD marketed under the name “Si75” by the company Evonik, polyorganosiloxanes, mercaptosilanes, blocked mercaptosilanes, such as S-(3-(triethoxysilyl)propyl)octanethioate marketed by the company Momentive under the name “NXT Silane”. More preferably, the organosilane is a polysulfurized organosilane.
Lorsque de la silice est utilisée, la teneur en agent de couplage dans la composition de la première couche du stratifié de l'invention peut aisément être ajustée par l'homme du métier. Typiquement le taux d'agent de couplage représente de 0,5% à 15% en poids par rapport à la quantité de silice.When silica is used, the content of coupling agent in the composition of the first layer of the laminate of the invention can easily be adjusted by those skilled in the art. Typically the level of coupling agent represents 0.5% to 15% by weight relative to the quantity of silica.
Le système de réticulation peut être tout type de système connu de l'homme de l'art dans le domaine des compositions de caoutchouc pour pneumatique. Il peut notamment être à base de soufre, et/ou de peroxyde et/ou de bismaléimides.The crosslinking system can be any type of system known to those skilled in the art in the field of rubber compositions for tires. It may in particular be based on sulfur, and/or peroxide and/or bismaleimides.
De manière préférentielle, le système de réticulation est à base de soufre, on parle alors d'un système de vulcanisation. Le soufre peut être apporté sous toute forme, notamment sous forme de soufre moléculaire, ou d'un agent donneur de soufre. Au moins un accélérateur de vulcanisation est également préférentiellement présent, et, de manière optionnelle, préférentielle également, on peut utiliser divers activateurs de vulcanisation connus tels qu'oxyde de zinc, acide stéarique ou composé équivalent tels que les sels d'acide stéarique et sels de métaux de transition, dérivés guanidiques (en particulier diphénylguanidine), ou encore des retardateurs de vulcanisation connus.Preferably, the crosslinking system is based on sulfur, we then speak of a vulcanization system. The sulfur can be provided in any form, in particular in the form of molecular sulfur, or of a sulfur-donating agent. At least one vulcanization accelerator is also preferably present, and, optionally, also preferentially, various known vulcanization activators can be used such as zinc oxide, stearic acid or equivalent compound such as stearic acid salts and salts. transition metals, guanidic derivatives (in particular diphenylguanidine), or even known vulcanization retarders.
Le soufre est utilisé à un taux préférentiel compris entre 0.3 pce et 10 pce, plus préférentiellement entre 0.3 et 5 pce. L'accélérateur primaire de vulcanisation est utilisé à un taux préférentiel compris entre 0.5 et 10 pce, plus préférentiellement compris entre 0.5 et 5 pce.Sulfur is used at a preferential rate of between 0.3 pce and 10 pce, more preferably between 0.3 and 5 pce. The primary vulcanization accelerator is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5 phr.
On peut utiliser comme accélérateur tout composé susceptible d'agir comme accélérateur de vulcanisation des élastomères diéniques en présence de soufre, notamment des accélérateurs du type thiazoles ainsi que leurs dérivés, des accélérateurs de types sulfénamides, thiurames, dithiocarbamates, dithiophosphates, thiourées et xanthates. A titre d'exemples de tels accélérateurs, on peut citer notamment les composés suivants : disulfure de 2-mercaptobenzothiazyle (en abrégé "MBTS"), N-cyclohexyl-2-benzothiazyle sulfénamide ("CBS"), N,N-dicyclohexyl-2-benzothiazyle sulfénamide ("DCBS"), N-ter-butyl-2-benzothiazyle sulfénamide ("TBBS"), N-ter-butyl-2-benzothiazyle sulfénimide ("TBSI"), disulfure de tetrabenzylthiurame ("TBZTD"), dibenzyldithiocarbamate de zinc ("ZBEC") et les mélanges de ces composés.Any compound capable of acting as an accelerator for the vulcanization of diene elastomers in the presence of sulfur can be used as an accelerator, in particular accelerators of the thiazole type as well as their derivatives, accelerators of the sulfenamide, thiuram, dithiocarbamate, dithiophosphate, thiourea and xanthate types. As examples of such accelerators, the following compounds may be cited in particular: 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS"), N-cyclohexyl-2-benzothiazyl sulfenamide ("CBS"), N,N-dicyclohexyl- 2-benzothiazyl sulfenamide ("DCBS"), N-ter-butyl-2-benzothiazyl sulfenamide ("TBBS"), N-ter-butyl-2-benzothiazyl sulfenimide ("TBSI"), tetrabenzylthiuram disulfide ("TBZTD") , zinc dibenzyldithiocarbamate (“ZBEC”) and mixtures of these compounds.
La composition de caoutchouc utile aux besoins de l'invention peut comporter également tout ou partie des additifs usuels habituellement utilisés dans les compositions d'élastomères destinées à être utilisées dans un pneumatique, comme par exemple des agents de mise en oeuvre, des plastifiants, des pigments, des agents de protection tels que cires anti-ozone, anti-ozonants chimiques, anti-oxydants. De préférence, la composition de caoutchouc comprend un plastifiant. Comme plastifiants conviennent tous les plastifiants conventionnellement utilisés dans les pneumatiques. A ce titre, on peut citer les huiles préférentiellement non aromatiques ou très faiblement aromatiques choisies dans le groupe constitué par les huiles naphténiques, les huiles paraffiniques, les huiles MES, les huiles TDAE, les huiles végétales, les plastifiants éthers, les plastifiants esters.The rubber composition useful for the purposes of the invention may also comprise all or part of the usual additives usually used in elastomer compositions intended to be used in a tire, such as for example processing agents, plasticizers, pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants. Preferably, the rubber composition comprises a plasticizer. All plasticizers conventionally used in tires are suitable as plasticizers. In this respect, we can cite oils preferably non-aromatic or very weakly aromatic chosen from the group consisting of naphthenic oils, paraffinic oils, MES oils, TDAE oils, vegetable oils, ether plasticizers, ester plasticizers.
Les compositions conformes à l'invention peuvent être fabriquées dans des mélangeurs appropriés, en utilisant deux phases de préparation successives bien connues de l'homme du métier :
- une première phase de travail ou malaxage thermomécanique (phase dite « non-productive »), qui peut être conduite en une seule étape thermomécanique au cours de laquelle on introduit, dans un mélangeur approprié tel qu'un mélangeur interne usuel (par exemple de type 'Banbury'), tous les constituants nécessaires, notamment la matrice élastomérique, la charge renforçante, les éventuels autres additifs divers, à l'exception du système de réticulation. L'incorporation de la charge éventuelle à l'élastomère peut être réalisée en une ou plusieurs fois en malaxant thermomécaniquement. Dans le cas où la charge est déjà incorporée en totalité ou en partie à l'élastomère sous la forme d'un mélange-maître (« masterbatch » en anglais) comme cela est décrit par exemple dans les demandes
WO 97/36724 WO 99/16600 - une seconde phase de travail mécanique (phase dite « productive »), qui est réalisée dans un mélangeur externe tel qu'un mélangeur à cylindres, après refroidissement du mélange obtenu au cours de la première phase non-productive jusqu'à une plus basse température, typiquement inférieure à 120°C, par exemple entre 40°C et 100°C. On incorpore alors le système de réticulation, et le tout est alors mélangé pendant quelques minutes, par exemple entre 5 et 15 min.
- a first working phase or thermomechanical mixing (so-called “non-productive” phase), which can be carried out in a single thermomechanical step during which we introduce, into a suitable mixer such as a usual internal mixer (for example of the type 'Banbury'), all the necessary constituents, in particular the elastomeric matrix, the reinforcing filler, any other various additives, with the exception of the crosslinking system. The incorporation of the possible filler into the elastomer can be carried out in one or more times by thermomechanical mixing. In the case where the filler is already incorporated in whole or in part into the elastomer in the form of a masterbatch (“masterbatch” in English) as described for example in the applications
WO 97/36724 WO 99/16600 - a second phase of mechanical work (called “productive” phase), which is carried out in an external mixer such as a roller mixer, after cooling the mixture obtained during the first non-productive phase to a lower temperature , typically below 120°C, for example between 40°C and 100°C. The crosslinking system is then incorporated, and everything is then mixed for a few minutes, for example between 5 and 15 min.
De telles phases ont été décrites par exemple dans les demandes
La composition finale ainsi obtenue est ensuite calandrée par exemple sous la forme d'une feuille ou d'une plaque, notamment pour une caractérisation au laboratoire, ou encore extrudée (ou co-extrudée avec une autre composition de caoutchouc) sous la forme d'un semi-fini (ou profilé) de caoutchouc utilisable par exemple comme flanc de pneumatique. Ces produits peuvent ensuite être utilisés pour la fabrication de pneumatiques, selon les techniques connues de l'homme du métier.The final composition thus obtained is then calendered for example in the form of a sheet or a plate, in particular for characterization in the laboratory, or even extruded (or co-extruded with another rubber composition) in the form of a semi-finished (or profile) of rubber usable for example as a tire sidewall. These products can then be used for the manufacture of tires, according to techniques known to those skilled in the art.
La composition peut être soit à l'état cru (avant réticulation ou vulcanisation), soit à l'état cuit (après réticulation ou vulcanisation), peut être un produit semi-fini qui peut être utilisé dans un pneumatique.The composition can be either in the raw state (before crosslinking or vulcanization), or in the cooked state (after crosslinking or vulcanization), and can be a semi-finished product which can be used in a tire.
La réticulation (ou cuisson), le cas échéant la vulcanisation, est conduite de manière connue à une température généralement comprise entre 130°C et 200°C, pendant un temps suffisant qui peut varier par exemple entre 5 et 90 min en fonction notamment de la température de cuisson, du système de réticulation adopté et de la cinétique de réticulation de la composition considérée.The crosslinking (or cooking), where appropriate the vulcanization, is carried out in a known manner at a temperature generally between 130°C and 200°C, for a sufficient time which can vary for example between 5 and 90 min depending in particular on the cooking temperature, the crosslinking system adopted and the crosslinking kinetics of the composition considered.
La présente invention a également pour objet un pneumatique comprenant une composition de caoutchouc selon l'invention.The present invention also relates to a tire comprising a rubber composition according to the invention.
De préférence, la composition selon l'invention est présente au moins dans un flanc du pneumatique selon l'invention. Avantageusement, cette composition est présente exclusivement dans les flancs du pneumatique.Preferably, the composition according to the invention is present at least in one sidewall of the tire according to the invention. Advantageously, this composition is present exclusively in the sidewalls of the tire.
Le pneumatique selon l'invention peut être destiné à équiper des véhicules à moteur de type tourisme, SUV ("Sport Utility Vehicles"), ou deux roues (notamment motos), ou avions, ou encore des véhicules industriels choisis parmi camionnettes, « Poids-lourd » - c'est-à-dire métro, bus, engins de transport routier (camions, tracteurs, remorques), véhicules hors-la-route tels qu'engins agricoles ou de génie civil -, et autres.The tire according to the invention can be intended to equip motor vehicles of the tourism type, SUV ("Sport Utility Vehicles"), or two wheels (in particular motorcycles), or airplanes, or even industrial vehicles chosen from vans, "Weight -heavy” - that is to say metro, bus, road transport vehicles (trucks, tractors, trailers), off-road vehicles such as agricultural or civil engineering vehicles -, and others.
La caractérisation spectrale et les mesures de la microstructure des copolymères d'éthylène et du 1,3-myrcène sont réalisées par spectroscopie de Résonance Magnétique Nucléaire (RMN).The spectral characterization and measurements of the microstructure of the copolymers of ethylene and 1,3-myrcene are carried out by Nuclear Magnetic Resonance (NMR) spectroscopy.
Spectromètre : Pour ces mesures, un spectromètre Bruker Avance III HD 400 MHz est utilisé, équipé d'une sonde Bruker cryo-BBFO z-grad 5 mm.Spectrometer: For these measurements, a Bruker Avance III HD 400 MHz spectrometer is used, equipped with a Bruker cryo-BBFO z-grad 5 mm probe.
Expériences : Les expériences 1H sont enregistrées à l'aide d'une impulsion radiofréquence avec un angle de basculement de 30°, le nombre de répétitions est de 128 avec un délai de recyclage de 5 secondes. Les expériences RMN de corrélation 1H-13C HSQC (Heteronuclear Single Quantum Cohérence) et HMBC (Heteronuclear Multiple-Bond Corrélation) sont enregistrées avec un nombre de répétition de 128 et un nombre d'incréments de 128. Les expériences sont réalisées à 25°C.Experiments: 1H experiments are recorded using a radio frequency pulse with a flip angle of 30°, the number of repetitions is 128 with a recycle delay of 5 seconds. The 1H-13C HSQC (Heteronuclear Single Quantum Coherence) and HMBC (Heteronuclear Multiple-Bond Correlation) NMR experiments are recorded with a number of repetitions of 128 and a number of increments of 128. The experiments are carried out at 25°C .
Préparation de l'échantillon : 25 mg d'échantillon sont solubilisés dans 1 mL de chloroforme deutéré (CDCl3).Preparation of the sample: 25 mg of sample are dissolved in 1 mL of deuterated chloroform (CDCl 3 ).
Calibration de l'échantillon : Les axes des déplacements chimiques 1H et 13C sont calibrés par rapport à l'impureté protonée du solvant (CHCl3) à δ1H = 7,2 ppm et δ13C = 77 ppm.Calibration of the sample: The chemical shift axes 1 H and 13 C are calibrated against the protonated impurity of the solvent (CHCl 3 ) at δ 1H = 7.2 ppm and δ 13C = 77 ppm.
Attribution spectrale pour les copolymères d'éthylène et du 1,3-myrcène : Dans les représentations A, B, C ci-dessous, les symboles R1 et R2 représentent les points de rattachement de l'unité à la chaîne polymère. Les signaux des formes d'insertion du 1,3-diène A, B et C ont été observés sur les différents spectres enregistrés. D'après
- Ethylène : signal à 1,2 ppm correspondant à 4 protons
- Myrcène total : signal n°1 (1,59 ppm) correspondant à 6 protons
- Forme A : signal n°7 (4,67 ppm) correspondant à 2 protons
- Forme B : signal n°8' (5,54 ppm) correspondant à 1 proton
- Ethylene: signal at 1.2 ppm corresponding to 4 protons
- Total myrcene: signal n°1 (1.59 ppm) corresponding to 6 protons
- Form A: signal n°7 (4.67 ppm) corresponding to 2 protons
- Form B: signal n°8' (5.54 ppm) corresponding to 1 proton
La quantification de la microstructure est réalisée en pourcentage molaire (%molaire) comme suit : %molaire d'un motif = intégrale 1H d'un motif * 100 / Σ (intégrales 1H de chaque motif).
La température de transition vitreuse est mesurée au moyen d'un calorimètre différentiel ("Differential Scanning Calorimeter") selon la norme ASTM D3418 (1999).The glass transition temperature is measured using a differential scanning calorimeter according to standard ASTM D3418 (1999).
Dans la synthèse de copolymères conformes à l'invention, le 1,3-diène utilisé est le myrcène, 1,3-diène de formule (I) dans lequel R est un groupe hydrocarboné ayant 6 atomes de carbone : CH2-CH2-CH=CMe2.In the synthesis of copolymers according to the invention, the 1,3-diene used is myrcene, 1,3-diene of formula (I) in which R is a hydrocarbon group having 6 carbon atoms: CH 2 -CH 2 -CH=CMe 2 .
Tous les réactifs sont obtenus commercialement exceptés les métallocènes. [{Me2SiFlu2Nd(µ-BH4)2Li(THF)}] est préparé selon le mode opératoire décrit dans la demande de brevet
Le butyloctylmagnésium BOMAG (20% dans l'heptane, C = 0,88 mol.L-1) provient de Chemtura et est stocké dans un tube de Schlenk sous atmosphère inerte. L'éthylène, de qualité N35, provient de la société Air Liquide et est utilisé sans purification préalable. Le myrcène (pureté ≥ 95%) est obtenu chez Sigma-Aldrich.BOMAG butyloctylmagnesium (20% in heptane, C = 0.88 mol.L -1 ) comes from Chemtura and is stored in a Schlenk tube under an inert atmosphere. The ethylene, N35 quality, comes from the company Air Liquide and is used without prior purification. Myrcene (purity ≥ 95%) is obtained from Sigma-Aldrich.
Dans un réacteur contenant à 80°C du méthylcyclohexane, de l'éthylène (Et) et du butadiène (Bd) dans les proportions indiquées dans le Tableau 2, on ajoute du butyloctylmagnésium (BOMAG) pour neutraliser les impuretés du réacteur, puis le système catalytique (voir Tableau 2). A ce moment, la température de réaction est régulée à 80°C et la réaction de polymérisation démarre. La réaction de polymérisation se déroule à une pression constante de 8 bars. Le réacteur est alimenté tout au long de la polymérisation en éthylène et en butadiène dans les proportions définies dans le Tableau 2. La réaction de polymérisation est stoppée par refroidissement, dégazage du réacteur et ajout d'éthanol. Un anti-oxydant est ajouté à la solution de polymère. Le copolymère est récupéré par séchage en étuve sous vide jusqu'à masse constante. Le système catalytique est un système catalytique préformé. Il est préparé dans le méthylcyclohexane à partir d'un métallocène, le [Me2SiFlu2Nd(µ-BH4)2Li(THF)], d'un co-catalyseur, le butyloctylmagnésium (BOMAG), et d'un monomère de préformation, le 1,3-butadiène, dans les teneurs indiquées dans le Tableau 2. Il est préparé selon une méthode de préparation conforme au paragraphe II. 1 de la demande de brevet
Dans un réacteur contenant à 80°C du méthylcyclohexane, de l'éthylène et du myrcène (My) dans les proportions indiquées dans le Tableau 2, on ajoute du butyloctylmagnésium (BOMAG) pour neutraliser les impuretés du réacteur, puis le système catalytique (voir Tableau 2). A ce moment, la température de réaction est régulée à 80°C et la réaction de polymérisation démarre. La réaction de polymérisation se déroule à une pression constante de 8 bars. Le réacteur est alimenté tout au long de la polymérisation en éthylène et en myrcène dans les proportions définies dans le Tableau 2. La réaction de polymérisation est stoppée par refroidissement, dégazage du réacteur et ajout d'éthanol. Un anti-oxydant est ajouté à la solution de polymère. Le copolymère est récupéré par séchage en étuve sous vide jusqu' à masse constante. Le système catalytique est un système catalytique préformé. Il est préparé dans le méthylcyclohexane à partir d'un métallocène, le [Me2SiFlu2Nd(µ-BH4)2Li(THF)], d'un co-catalyseur, le butyloctylmagnésium (BOMAG), et d'un monomère de préformation, le 1,3-butadiène, dans les teneurs indiquées dans le Tableau 2. Il est préparé selon une méthode de préparation conforme au paragraphe II. 1 de la demande de brevet
La microstructure des polymères et leurs propriétés figurent dans les Tableaux 3 et 4.
Dans les exemples qui suivent, les compositions caoutchouteuses ont été réalisées comme décrit au point II-5 ci-dessus. En particulier, la phase « non-productive » a été réalisée dans un mélangeur de 3 litres pendant 5 minutes, pour une vitesse moyenne de palettes de 50 tours par minute jusqu'à atteindre une température maximale de tombée de 160°C. La phase « productive » a été réalisée dans un outil à cylindre à 23°C pendant 10 minutes.In the examples which follow, the rubber compositions were produced as described in point II-5 above. In particular, the “non-productive” phase was carried out in a 3 liter mixer for 5 minutes, for an average paddle speed of 50 revolutions per minute until reaching a maximum drop temperature of 160°C. The “productive” phase was carried out in a cylinder tool at 23°C for 10 minutes.
L'adhésion de plusieurs compositions de caoutchouc comprenant un mélange de caoutchouc naturel et de copolymère d'éthylène et de 1,3-diène sur une composition à base de caoutchouc naturel a été comparée en fonction de la nature et du taux du copolymère d'éthylène et de 1,3-diène.The adhesion of several rubber compositions comprising a mixture of natural rubber and copolymer of ethylene and 1,3-diene on a composition based on natural rubber was compared as a function of the nature and the level of the copolymer of ethylene and 1,3-diene.
Les mesures d'adhésion ont réalisées par un test dit de pelage en T ou aussi appelé pelage à 180°. Les éprouvettes de pelage ont réalisées par mise en contact des deux couches (les compositions constitutives des couches étant à l'état cru) dont l'adhésion doit être testée. Une amorce de rupture a été insérée entre les deux couches. Chacune des couches a été renforcée par une nappe composite qui limite la déformation des dites couches sous traction.The adhesion measurements were carried out using a so-called T-peel test or also called 180° peel. The peel specimens were produced by bringing the two layers into contact (the constituent compositions of the layers being in the raw state) whose adhesion must be tested. A rupture starter was inserted between the two layers. Each of the layers was reinforced by a composite layer which limits the deformation of said layers under tension.
L'éprouvette une fois assemblée a été portée à 150°C sous une pression de 16 bars pendant 30 minutes. Des bandes de 30 mm de largeur ont ensuite été découpées au massicot. Les deux côtés de l'amorce de rupture ont été ensuite placées dans les mors d'une machine de traction de marque « Instron ». Les essais ont été réalisés à 20°C et à une vitesse de traction de 100 mm/min. On a enregistré les efforts de traction et on norme ceux-ci par la largeur de l'éprouvette. On a obtenu une courbe de force par unité de largeur (en N/mm) en fonction du déplacement de traverse mobile de la machine de traction (entre 0 et 200 mm). La valeur d'adhésion retenue correspond à la propagation de la rupture au sein de l'éprouvette et donc à la valeur stabilisée moyenne de la courbe. Les valeurs d'adhésion des exemples ont été normées par rapport au témoin (base 100). Un indice supérieur à 100 indique une plus forte amélioration de l'adhésion.Once assembled, the test piece was heated to 150°C under a pressure of 16 bars for 30 minutes. Strips 30 mm wide were then cut with a paper cutter. The two sides of the rupture starter were then placed in the jaws of an “Instron” brand traction machine. The tests were carried out at 20°C and at a traction speed of 100 mm/min. The tensile forces were recorded and these were standardized by the width of the specimen. We obtained a curve of force per unit of width (in N/mm) as a function of the displacement of the moving crossmember of the traction machine (between 0 and 200 mm). The adhesion value retained corresponds to the propagation of the rupture within the specimen and therefore to the average stabilized value of the curve. The adhesion values of the examples were normalized in relation to the control (base 100). An index greater than 100 indicates greater improvement in adherence.
L'adhésion de compositions C1 à C6, conformes à l'invention, a été comparée aux témoins T1 à T6 non-conformes à l'invention qui diffèrent respectivement des compositions C1 à C6 uniquement par la nature du 1,3-diène : 1,3 diène de formule (I) pour les compositions C1 à C6 et 1,3-butadiène pour les compositions T1 à T6 (les élastomères E1 et E2 ont été préparés selon le procédé décrit au point III.2 ci-dessus).The adhesion of compositions C1 to C6, in accordance with the invention, was compared to controls T1 to T6 not in accordance with the invention which differ respectively from compositions C1 to C6 only by the nature of the 1,3-diene: 1 .3 diene of formula (I) for compositions C1 to C6 and 1,3-butadiene for compositions T1 to T6 (elastomers E1 and E2 were prepared according to the process described in point III.2 above).
La couche à base de caoutchouc naturel sur laquelle l'adhésion a été testée correspond à une composition classiquement utilisée en couche interne de pneumatique, telle qu'une nappe carcasse ou une sous-couche de bande de roulement, comprenant 100 pce de caoutchouc naturel.The natural rubber-based layer on which adhesion was tested corresponds to a composition conventionally used as an internal tire layer, such as a carcass ply or a tread underlayer, comprising 100 phr of natural rubber.
Le Tableau 5 présente les compositions testées (en pce), ainsi que les résultats obtenus.
(2) Noir de carbone N234 selon la norme ASTM D-1765-2017
(3) Silice « Zeosil 1165MP » commercialisée par Solvay
(4) Silane liquide triethoxysilylpropyltetrasulfure (TESPT) « Si69 » de la société Evonik
(5) Diphénylguanidine « Perkacit DPG » de la société Flexsys
(6) N-1,3-diméthylbutyl-N-phényl-para-phenyldiamine « Santoflex 6-PPD » de la société Flexsys
(7) Cire anti-ozone « VARAZON 4959 » de la société Sasol Wax
(8) Oxyde de Zinc de grade industriel de la société Umicore
(9) N-cyclohexyl-2-benzothiazol-sulfénamide « Santocure CBS » de la société Flexsys
(2) Carbon black N234 according to ASTM D-1765-2017
(3) Silica “Zeosil 1165MP” marketed by Solvay
(4) Silane liquid triethoxysilylpropyltetrasulfide (TESPT) “Si69” from the company Evonik
(5) Diphenylguanidine “Perkacit DPG” from the company Flexsys
(6) N-1,3-dimethylbutyl-N-phenyl-para-phenyldiamine “Santoflex 6-PPD” from the company Flexsys
(7) Anti-ozone wax “VARAZON 4959” from the company Sasol Wax
(8) Industrial grade Zinc Oxide from Umicore
(9) N-cyclohexyl-2-benzothiazol-sulfenamide “Santocure CBS” from the company Flexsys
Ces résultats montrent que l'utilisation d'une composition de caoutchouc conforme à l'invention comprenant un copolymère d'éthylène et de 1,3-diène de formule (I) permet d'améliorer l'adhésion sur une composition diénique par rapport à une composition de caoutchouc non conforme à l'invention comprenant un copolymère d'éthylène et de 1,3-diène.These results show that the use of a rubber composition according to the invention comprising a copolymer of ethylene and 1,3-diene of formula (I) makes it possible to improve adhesion on a diene composition compared to a rubber composition not in accordance with the invention comprising a copolymer of ethylene and 1,3-diene.
Claims (14)
- Rubber composition at least based on:- 5 to 95 phr of polyisoprene comprising a content by weight of 1,4-cis bonds of at least 90% of the weight of the polyisoprene,- 5 to 95 phr of copolymer of ethylene and of a 1,3-diene of formula (I), the ethylene units in the copolymer representing more than 50 mol% of the monomer units of the copolymer,
CH2=CR-CH=CH2 (I)
the symbol R representing a hydrocarbon chain having 3 to 20 carbon atoms, and- a crosslinking system. - Rubber composition according to Claim 1, wherein the copolymer contains ethylene units which represent between 50 mol% and 95 mol%, preferably from 60 mol% to 90 mol%, more preferably from 70 mol% to 85 mol%, of the monomer units of the copolymer.
- Rubber composition according to either one of the preceding claims, wherein the copolymer contains units of the 1,3-diene of 1,2 or 3,4 configuration which represent more than 50 mol% of the units of the 1,3-diene.
- Rubber composition according to any one of the preceding claims, wherein 1,3-diene is myrcene or β-famesene.
- Rubber composition according to any one of the preceding claims, wherein the copolymer has a glass transition temperature below -35°C, preferably between -90°C and -35°C.
- Rubber composition according to any one of the preceding claims, wherein the content of the copolymer is within a range extending from 15 to less than 50 phr.
- Rubber composition according to any one of the preceding claims, wherein the polyisoprene comprises a content by weight of 1,4-cis bonds of at least 98% of the weight of the polyisoprene.
- Rubber composition according to any one of the preceding claims, wherein the polyisoprene is selected from the group consisting of natural rubber, synthetic polyisoprenes and mixtures thereof; preferably the polyisoprene is a natural rubber.
- Rubber composition according to any one of the preceding claims, also comprising a reinforcing filler.
- Rubber composition according to Claim 9, wherein the reinforcing filler comprises mainly carbon black.
- Rubber composition according to Claim 9 or 10, wherein the content of reinforcing filler is within a range extending from 15 to 80 phr, preferably from 20 to 55 phr, preferably from 25 to 45 phr.
- Rubber composition according to any one of the preceding claims, wherein the content of the polyisoprene is within a range extending from more than 50 to 85 phr, the content of the copolymer is within a range extending from 15 to less than 50 phr, and comprising a reinforcing filler comprising mainly carbon black.
- Tyre comprising a rubber composition defined in any one of Claims 1 to 12.
- Tyre according to Claim 13, wherein the rubber composition defined in any one of Claims 1 to 12 is present in at least one sidewall of the tyre.
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| FR1914615A FR3104596B1 (en) | 2019-12-17 | 2019-12-17 | RUBBER COMPOSITION |
| PCT/FR2020/052354 WO2021123568A1 (en) | 2019-12-17 | 2020-12-09 | Rubber composition |
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| EP4076984A1 EP4076984A1 (en) | 2022-10-26 |
| EP4076984B1 true EP4076984B1 (en) | 2024-05-15 |
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| EP (1) | EP4076984B1 (en) |
| CN (1) | CN114829156B (en) |
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| FR3104487B1 (en) | 2019-12-17 | 2021-11-05 | Michelin & Cie | ELASTOMERIC LAMINATE |
| FR3136771B1 (en) * | 2022-06-21 | 2024-05-10 | Michelin & Cie | Rubber composition comprising a highly saturated diene elastomer |
| FR3136770B1 (en) * | 2022-06-21 | 2024-05-10 | Michelin & Cie | Rubber composition comprising a highly saturated diene elastomer |
| FR3136775B1 (en) * | 2022-06-21 | 2024-05-10 | Michelin & Cie | Rubber composition comprising a highly saturated diene elastomer |
| FR3136774B1 (en) * | 2022-06-21 | 2024-05-10 | Michelin & Cie | Rubber composition comprising a highly saturated diene elastomer |
| FR3136772B1 (en) * | 2022-06-21 | 2024-05-10 | Michelin & Cie | Rubber composition comprising a highly saturated diene elastomer |
| FR3136773B1 (en) * | 2022-06-21 | 2024-05-10 | Michelin & Cie | Rubber composition comprising a highly saturated diene elastomer |
| EP4316869A1 (en) * | 2022-08-01 | 2024-02-07 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tire and tire |
| FR3143032A1 (en) * | 2022-12-08 | 2024-06-14 | Compagnie Generale Des Etablissements Michelin | COMPOSITE FOR RUBBER ARTICLE |
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| FR3044662B1 (en) | 2015-12-03 | 2017-12-08 | Michelin & Cie | PREFORMED CATALYTIC SYSTEM COMPRISING RARE EARTH METALLOCENE |
| FR3054220A1 (en) | 2016-07-25 | 2018-01-26 | Compagnie Generale Des Etablissements Michelin | PREFORMED CATALYTIC SYSTEM COMPRISING RARE EARTH METALLOCENE |
| JP7069688B2 (en) * | 2017-12-18 | 2022-05-18 | 住友ゴム工業株式会社 | Rubber composition for tires and pneumatic tires |
| FR3078973B1 (en) * | 2018-03-19 | 2020-04-03 | Compagnie Generale Des Etablissements Michelin | COPOLYMER OF ETHYLENE AND A 1,3-DIENE |
-
2019
- 2019-12-17 FR FR1914615A patent/FR3104596B1/en active Active
-
2020
- 2020-12-09 CN CN202080088304.1A patent/CN114829156B/en active Active
- 2020-12-09 US US17/786,348 patent/US20230059504A1/en active Pending
- 2020-12-09 WO PCT/FR2020/052354 patent/WO2021123568A1/en unknown
- 2020-12-09 EP EP20842716.1A patent/EP4076984B1/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2682423B1 (en) * | 2011-03-01 | 2016-10-19 | Bridgestone Corporation | Rubber composition, rubber composition for tire sidewall, crosslinked rubber composition, and tire |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114829156A (en) | 2022-07-29 |
| WO2021123568A1 (en) | 2021-06-24 |
| US20230059504A1 (en) | 2023-02-23 |
| FR3104596A1 (en) | 2021-06-18 |
| EP4076984A1 (en) | 2022-10-26 |
| FR3104596B1 (en) | 2021-11-12 |
| CN114829156B (en) | 2023-11-10 |
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